Journal of The Electrochemical Society, 152 共1兲 A205-A209 共2005兲 A205

0013-4651/2004/152共1兲/A205/5/$7.00 © The Electrochemical Society, Inc.

Solvent-Free Composite PEO-Ceramic FiberÕMat Electrolytes

for Lithium Secondary Cells
Chunsheng Wang,a,*,z Xiang-Wu Zhang,b,** and A. John Applebyb,*
a
Center for Manufacturing Research and Department of Chemical Engineering, Tennessee Technological
University, Cookeville, Tennessee 38505, USA
b
Center for Electrochemical Systems and Hydrogen Research, Texas Engineering Experiment Station, Texas
A&M University, College Station, Texas 77843-3402, USA

Solvent-free composite poly共ethylene oxide兲 共PEO兲-ceramic fiber or mat electrolytes with high ionic conductivity and good
interfacial stability have been developed using high-ionic-conductivity La0.55Li0.35TiO3 fibers and mats. The conducting ceramic
fibers can penetrate the cross section of the electrolyte film to provide long-range lithium-ion transfer channels, thus producing
composite electrolytes with high conductivity. In this work, a maximum room-temperature conductivity of 5.0 ⫻ 10⫺4 S cm⫺1
was achieved for 20 wt % La0.55Li0.35TiO3 fiber in a PEO-LiN共SO2 CF2 CF3 ) 2 mixture containing 12.5 wt % Li⫹ in PEO. The
maximum transference number obtained was 0.7. The ceramic fibers in this composite electrolyte are coated by a very thin PEO
layer, which is sufficient to provide good interfacial stability with lithium-ion and lithium-metal anodes.
© 2004 The Electrochemical Society. 关DOI: 10.1149/1.1828952兴 All rights reserved.

Manuscript submitted May 17, 2004; revised manuscript received June 18, 2004. Available electronically December 6, 2004.

Solvent-free all-solid-state rechargeable lithium secondary cells
have been studied extensively in recent years for cellular telephones,
laptop computers, electric and hybrid vehicles, and aerospace appli-
cations. In a solid-state lithium cell, solid electrolytes serve both as
ionic conductor and separator. Therefore, they must meet require-
ments of high ionic conductivity, high lithium ion transference num-
ber, a wide electrochemical stability window, easy processability,
and acceptable thermal and mechanical properties. Electrolytes
based on poly共ethylene oxide兲 共PEO兲 form dimensionally stable
films and show high chemical stability to reduction, but have room-
temperature conductivities that are too low (10⫺7 to 10⫺8 S-cm⫺1兲
for most applications. Certain ceramics and glasses show much
higher Li-ion conductivity. Lithium lanthanum titanate ceramic
(La0.55Li0.35TiO3 ) has the highest solid-state Li⫹ conductivity re-
ported to date (⬃10⫺3 S-cm⫺1兲 at room temperature.1-4 Its conduc-
tivity of 1.8 ⫻ 10⫺5 S-cm⫺1 at ⫺50°C is higher than that of typical
PEO compositions at 25°C. Unfortunately, La0.55Li0.35TiO3 ceramic
cannot be directly used in lithium secondary cells because it is
chemically unstable below 1.5 V vs. Li0 due to Ti共IV兲 to Ti共III兲
reduction.1,3 To enhance the chemical stability of La0.55Li0.35TiO3 at
low electrochemical potentials, thin layers of chemically stable
PEO-salt complexes or ceramics such as LiPON have been placed
between La0.55Li0.35TiO3 plates and lithium metal or lithiated graph-
ite anodes.4,5 The conductivities of these composite electrolytes can
reach 10⫺4 S-cm⫺1. However, their inflexibility and poor mechani-
cal strength do not allow easy construction of suitable electrochemi-
cal secondary cells. Another possible design puts high-conductivity
ceramic particles into a PEO-salt complex to form a composite solid
polymer electrolyte.6 However, poorly conducting interparticle con-
tact results in little improvement in conductivity over that of PEO
alone.
The approach suggested here to achieve high ionic conductivity
combined with chemical and mechanical stability is the use of
La0.55Li0.35TiO3 fibers and/or mats combined with PEO in which an
additional very thin PEO layer is coated on the La0.55Li0.35TiO3
surface. A parallel approach, that of filling PEO with nonconducting
ceramic 共or glass兲 fibers and mats to reinforce polymer electrolytes,
has been reported.7-9 Incorporation of nonconducting ceramic fibers
and mats into polymer electrolytes can enhance the mechanical
properties of the electrolyte membranes, but decreases the ionic con-
ductivity of the polymer electrolytes. However, La0.55Li0.35TiO3
fiber-PEO electrolytes not only have good mechanical strength but
* Electrochemical Society Active Member.
** Electrochemical Society Student Member.
z
E-mail: cswang@tntech.edu
also have high conductivity because the conducting fibers can pen-
etrate the electrolyte film cross section to provide long-range Li⫹
transfer channels. The conducting fibers in La0.55Li0.35TiO3 mat-
PEO electrolytes have a similar function, but their woven pattern
provides better bridging.
Experimental
Electrolyte preparation.—PEO polymer 共Aldrich; Mw 600,000
Da兲 was dried under vacuum at 50°C for 24 h. Lithium bis共perfluo-
roethylsulfonyl兲 imide 关 LiN共SO2 CF2 CF3 ) 2 ; 3M Company兴 and
LiClO4 共Aldrich兲 were dried at 120°C for 24 h. La0.55Li0.35TiO3
(9.1 ⫻ 10⫺4 S-cm⫺1兲 particles less than 1 ␮m were prepared from
Li2 CO3 , La2 O3 , and TiO2 starting materials using Inaguma’s solid-
state reaction method.1 Stoichiometric amounts of these powders
were ground together in an agate mortar and calcined at 800°C for 4
h to eliminate CO2 . The heated powder was ballmilled with ethanol
for 1 day, and heated again at 800°C for 2 h. The ballmilled powder
was then sieved through a #325 mesh for fiber and mat preparation.
La0.55Li0.35TiO3 powders for filling PEO-LiClO4 electrolytes were
sintered at 1325°C for 2 h. The crystalline phases of La0.55Li0.35TiO3
powders were identified by X-ray diffraction 共XRD兲 analysis at
room temperature using Cu K␣ radiation. The 2␪ range analyzed
was 10-90°, and the scan rate was 2.0° per second. The particle size
was observed by scanning electron microscopy 共SEM兲 images using
a Jeol JSM-6400 microscope equipped with a Noran 1-2 energy-
dispersive spectrometer. A 15 kV beam was employed
to generate the backscattered-electron images. Sintered
La0.55Li0.35TiO3 fibers of two different diameters 共15 and 250 ␮m兲
were produced by Advanced Cerametrics, Inc. using its Viscous Sus-
pension Spinning Process 共VSSP兲 method.10 In the VSSP method,
La0.55Li0.35TiO3 powders were first dispersed in water to give a
slurry, which was then mixed with viscose, i.e., cellulose in aqueous
sodium hydroxide solution. The mixture was then pumped through
spinneret holes into a low-concentration sulfuric acid bath to form
particulate La0.55Li0.35TiO3 -loaded cellulose 共rayon兲 fibers. This was
followed by sintering at 1325°C for 2 h. To fabricate
La0.55Li0.35TiO3 mats, cellulose fibers loaded with La0.55Li0.35TiO3
particles were first woven into cloth-like mats, then sintered at
1350°C for 2 h.
La0.55Li0.35TiO3 fiber-PEO composite electrolytes were prepared
from acetonitrile dispersions of weighed quantities of fiber, lithium
salt, and PEO to give 12.5 wt % Li⫹ in the PEO matrix. These were
ultrasonically vibrated for 8.0 h, cast onto poly共tetrafluoroethylene兲
films, and dried in air for 24 h, then vacuum dried at 25°C, followed
by 80°C, each for 24 h. La0.55Li0.35TiO3 mat-PEO composite elec-
trolytes were prepared by dropping a fresh solution of PEO and
A206 Journal of The Electrochemical Society, 152 共1兲 A205-A209 共2005兲
Figure 1. XRD patterns of La0.55Li0.35TiO3 powders calcined at 800°C and
sintered at 1325°C.
lithium salt in the same wt % ratio dissolved in acetonitrile into
La0.55Li0.35TiO3 mats, followed by rigorous drying as above.
Electrochemical measurements.—The ionic conductivity of the
films was measured by electrochemical impedance spectroscopy
共EIS兲 using symmetrical two-electrode cells sandwiching a film be-
tween two stainless steel plate electrodes. Spectra were obtained by
sweeping from 65 kHz to 1 Hz with a Solartron FRA 1250 fre-
quency analyzer and a Solartron model 1286 electrochemical inter-
face. The high-frequency intercept of the Nyquist plot on the real
axis gives the resistance R of the electrolyte, from which the ionic
conductivity is calculated. Li⫹ transference number (tLi⫹) measure-
ments were conducted on symmetrical lithium/composite
electrolyte/lithium cells by using the method of Bruce and Vincent.11
The stability of the composite electrolyte-lithium electrode inter-
face was investigated by monitoring the time dependence of the
impedance of symmetrical Li/composite electrolyte/Li cells under
open-circuit conditions. This impedance measurement was obtained
by sweeping from 65 kHz to 0.01 Hz using the same equipment as
that for the ionic conductivity measurements.
Figure 2. SEM images of the La0.55Li0.35TiO3 particles prepared by solid-
state reaction.
Figure 3. A spool of green La0.55Li0.35TiO3 fiber of 15 ␮m diam.
Results and Discussion
Preparation of La2/3⫺xLi3xTiO3 particles, fibers, and mats.—
Figure 1 shows the XRD patterns of La0.55Li0.35TiO3 powders
calcined at 800°C and sintered at 1325°C. The powders calcined
at 800°C consist only of a mixture of La2 O3 , Li2 O, and TiO2 .
However, the sintered powders were La0.55Li0.35TiO3 , which has a
cubic perovskite-type structure. The XRD patterns of the sintered
La0.55Li0.35TiO3 powders are in agreement with the previously re-
ported XRD data of a ceramic with a similar composition.12
La0.55Li0.35TiO3 powder disks were cold-pressed and sintered at
1325°C for 2 h. Their conductivity determined by EIS was ca.
9.1 ⫻ 10⫺4 S-cm⫺1 at room temperature.
La0.55Li0.35TiO3 fibers and mats were made from ballmilled
La0.55Li0.35TiO3 particles using the VSSP method. Figure 2 shows
SEM images of the ballmilled La0.55Li0.35TiO3 particles used to pre-
pare fibers and mats. The particle size of La0.55Li0.35TiO3 was less
than 1 ␮m after ballmilling for 1 day. Some La0.55Li0.35TiO3 par-
ticles were agglomerated to form large porous particles of 2-3 ␮m
diam. La0.55Li0.35TiO3 -loaded cellulose fibers 共green fibers兲 of 15
and 250 ␮m diam were successfully made from ballmilled
La0.55Li0.35TiO3 particles. Figure 3 shows a spool of green
La0.55Li0.35TiO3 fiber of 15 ␮m diam, which was woven into a mat
共Fig. 4兲, then sintered at 1325°C for 2 h. Figure 5 shows sintered
La0.55Li0.35TiO3 15 ␮m diam fibers and sintered woven
La0.55Li0.35TiO3 mats.
Figure 4. Woven mats made from green La0.55Li0.35TiO3 fibers of 15 ␮m
diam.
 Journal of The Electrochemical Society, 152 共1兲 A205-A209 共2005兲
Figure 5. Sintered La0.55Li0.35TiO3 共a兲 fibers and 共b兲 mats.
Ionic conductivity of fiber-PEO electrolytes.—Perovskite oxides
of ABO3 type such as La0.67⫺x Li3x TiO3 have exceptional ionic con-
ductivity, first reported by Inaguma.1 However, ceramic membranes
formed from these materials are brittle, making them difficult to use
in secondary cells. The easiest way to give these materials flexibility
is to load particles of ceramic into PEO-salt complexes to form
composite polymer electrolytes, which have higher conductivity
than the host PEO electrolytes.6 In these conducting particle-PEO
composite electrolytes, ceramic particles are homogeneously dis-
persed in the PEO matrix, and hence are separated by relatively
thick polymer layers. The poorly conducting contacts between ce-
ramic particles prevent much improvement of conductivity over that
of the PEO host. However, conducting ceramic fibers can bridge the
gap in the electrolyte film cross section, and hence provide long-
range Li⫹ transfer channels. Figure 6 compares the ionic conductivi-
ties of electrolytes with 20 wt % La0.55Li0.35TiO3 particles and 20 wt
% La0.55Li0.35TiO3 250 ␮m diam fibers in PEO-LiN共SO2 CF2 CF3 ) 2 .
The fiber-PEO electrolyte has higher conductivity than the particle-
PEO electrolyte over the temperature range studied. The room-
temperature conductivity of 20 wt % La0.55Li0.35TiO3 fiber-PEO-
LiN共SO2 CF2 CF3 ) 2 electrolyte was 5.0 ⫻ 10⫺4 S-cm⫺1.
Figure 7 shows the temperature dependence of ionic conductivity
for 50 wt % La0.55Li0.35TiO3 fiber-PEO-LiClO4 electrolytes with dif-
ferent fiber diameters. Compared to thick fiber-PEO electrolytes,
those with thin fibers have a higher area-to-volume ratio in the elec-
trolyte film, giving higher conductivity over the whole temperature
range. Fiber diameter therefore plays an important role in determin-
ing the ionic conductivity of fiber-PEO composite electrolytes, as
does the choice of lithium salt. Figure 8 shows the temperature
dependence of ionic conductivity for 250 ␮m diam La0.55Li0.35TiO3
fiber-PEO-LiClO4 and -PEO-LiN共SO2 CF2 CF3 ) 2 electrolytes. Be-
cause the conductivity of La0.55Li0.35TiO3 fiber is not influenced by
the presence of the lithium salt, any changes in electrolyte conduc-
tivity must occur in the PEO matrix. LiN共SO2 CF2 CF3 ) 2 has large
anions which can influence the PEO polymer chain crystallization
Figure 6. Arrhenius plots for the ionic conductivity of 20 wt %
La0.55Li0.35TiO3 particle-PEO-LiN共SO2 CF2 CF3 ) 2 and 20 wt % 250 ␮m
diameter La0.55Li0.35TiO3 fiber-PEO-LiN共SO2 CF2 CF3 ) 2 composite
electrolytes.
A207
Figure 7. Arrhenius plots for the ionic conductivity of 50 wt %
La0.55Li0.35TiO3 fiber-PEO-LiClO4 composite electrolytes with differing fiber
diameters. Thin fiber: 15 ␮m, thick fiber: 250 ␮m.
process, promoting amorphous regions with increased ionic conduc-
tivity. Therefore, the PEO matrix conductivity still plays an impor-
tant role in the overall conductivity properties of these composite
electrolytes, although the conducting fibers dominate in Li⫹ transfer.
One disadvantage of PEO-based polymer electrolytes is that
polymer chain thermal motion can cause the amorphous PEO phase
to slowly recrystallize at room temperature, which results in a loss
of ionic conductivity during storage. Figure 9 shows the change in
the relative conductivity (␴/␴ 0 ) for PEO-LiN共SO2 CF2 CF3 ) 2 and 20
wt % La0.55Li0.35TiO3 fiber 共250 ␮m兲-PEO-LiN共SO2 CF2 CF3 ) 2 elec-
trolytes over a 35 day period at 25°C. The conductivity of
La0.55Li0.35TiO3 fiber, which penetrates the electrolyte cross section,
does not change much during storage. At the same time, the ceramic
fibers can also stabilize the conductivity of the PEO matrix by hin-
dering its recrystallization. Therefore, the conductivity loss of
La0.55Li0.35TiO3 fiber-PEO composite electrolyte is less than that of
the host polymer electrolyte.
Ionic conductivity and Li⫹ transference number of mat-PEO
electrolytes.—Fiber-PEO composite electrolytes have a higher con-
ductivity than particle-PEO electrolytes because La0.55Li0.35TiO3 fi-
bers can provide long-range Li⫹ transfer channels through the elec-
trolyte film. However, most fibers are parallel to the film plane;
hence, only some of the fibers can penetrate the electrolyte com-
pletely. Therefore, PEO host conductivity still plays an important
role in the overall conductivity of fiber-PEO composite electrolytes,
as is shown in Fig. 8. However, when the conducting fibers are
woven into mats, they can penetrate the film cross section more
readily. Figure 10 compares the ionic conductivies of 50 wt %
Figure 8. Arrhenius plots for the ionic conductivity of 20 wt %
La0.55Li0.35TiO3 250 ␮m diam fiber-PEO-LiClO4 and PEO-
LiN共SO2 CF2 CF3 ) 2 composite electrolytes.
A208 Journal of The Electrochemical Society, 152 共1兲 A205-A209 共2005兲
Figure 9. Relative conductivity (␴/␴ 0 ) vs. time for PEO-
LiN共SO2 CF2 CF3 ) 2 and 20 wt % 250 ␮m diameter La0.55Li0.35TiO3 fiber-
PEO-LiN共SO2 CF2 CF3 ) 2 composite electrolytes.
La0.55Li0.35TiO3 fiber-PEO-LiClO4 and 70 wt % La0.55Li0.35TiO3
mat-PEO-LiClO4 composite electrolytes. Fiber-PEO composite
electrolytes with higher than 50 wt % fiber content are easily torn
because the fibers are in parallel and the PEO matrix is not strong
enough for bonding. The fiber content 共70 wt %兲 of La0.55Li0.35TiO3
mat-PEO-LiClO4 electrolytes was obtained by weighing the
La0.55Li0.35TiO3 mat and PEO-LiClO4 used. From Fig. 10, it is
clearly seen that the mat-PEO composite electrolyte has higher con-
ductivity that the fiber-PEO electrolyte over the whole temperature
range studied because of its higher fiber content combined with its
regular weave pattern.
The addition of conducting particles only slightly improves the
Li⫹ transference number.6 However, the Li⫹ transference number
of La0.55Li0.35TiO3 mat-PEO-LiClO4 composite electrolyte was de-
termined to be about 0.7, much higher than the highest number
(t Li⫹ ⫽ 0.39) given by La0.55Li0.35TiO3 particle-filled PEO
electrolytes.6 The high Li⫹ transference number for the
La0.55Li0.35TiO3 mat-PEO-LiClO4 composite electrolyte was attrib-
uted to the large amount of Li⫹-conducting (t Li⫹ ⫽ 1.0)
La0.55Li0.35TiO3 mat in the composite electrolytes.
Interfacial stability with lithium electrode.—La0.55Li0.35TiO3 ce-
ramic reacts with lithium metal, reducing the tetravalent titanium
ions, and producing an electronic or electronic-ionic mixed
conductor.1 As a result, it is very important to prevent the direct
contact of ceramic and lithium anodes. In fiber-PEO and mat-PEO
composite electrolytes, the conducting ceramic is coated with a very
thin PEO-salt layer, which separates the ceramic and lithium elec-
trode. A 20 wt % La0.55Li0.35TiO3 fiber-PEO-LiN共SO2 CF2 CF3 ) 2 was
Figure 10. Arrhenius plots for ionic conductivities of 50 wt %
La0.55Li0.35TiO3 fiber-PEO-LiClO4 and 70 wt % La0.55Li0.35TiO3 mat-PEO-
LiClO4 composite electrolytes.
Figure 11. Interfacial resistances as a function of time for PEO-
LiN共SO2 CF2 CF3 ) 2 and 20 wt % 250 ␮m diam La0.55Li0.35TiO3 fiber-PEO-
LiN共SO2 CF2 CF3 ) 2 polymer electrolytes.
sandwiched between two lithium electrodes in a glove box. The
color of the sample did not change with time, indicating that no
reaction between La0.55Li0.35TiO3 ceramic and lithium metal oc-
curred, because the color changes from ivory to blue-black on
reduction.1
Any reduction of tetravalent titanium ions starts at the
electrolyte-electrode interface. The interfacial resistance between 20
wt % La0.55Li0.35TiO3 fiber-PEO-LiN共SO2 CF2 CF3 ) 2 composite elec-
trolyte and lithium electrode was monitored as a function of time, as
shown in Fig. 11. The time dependence of the interfacial resistance
for PEO-LiN共SO2 CF2 CF3 ) 2 polymer electrolyte is also shown. The
interfacial resistance of the latter electrolyte increases markedly at
first, then increases irregularly. The initial increase indicates forma-
tion of a passivation layer, and the subsequent irregular increase
shows that its structure is unstable. The addition of La0.55Li0.35TiO3
fiber should make the interfacial resistance more unstable if reaction
is occurring. However, Fig. 11 shows that La0.55Li0.35TiO3 fiber sta-
bilizes the interfacial resistance, indicating no interfacial reaction.
This interfacial stabilization is attributed to the ability of the
La0.55Li0.35TiO3 fiber surface to scavenge traces of residual impuri-
ties in a similar way to added nonconducting ceramic particles.13,14
Conclusions
High-ionic-conducting La0.55Li0.35TiO3 fibers and mats were suc-
cessfully prepared using the VSSP method. La0.55Li0.35TiO3 fibers in
fiber-PEO and mat-PEO composite electrolytes can penetrate the
electrolyte film, and hence provide long-range Li⫹ transfer channels.
La0.55Li0.35TiO3 mat-PEO composite electrolyte has higher conduc-
tivity than fiber-PEO electrolyte because of the woven pattern and
higher fiber content. The fiber diameter and the salt type also play an
important role in the overall conductivity properties of composite
electrolytes.
The reaction between La0.55Li0.35TiO3 ceramic and lithium an-
odes is also prevented by the thin PEO-salt layer on the fiber sur-
face. Therefore, these composite electrolytes have good interfacial
stability with lithium metal and lithium-ion anodes.
Acknowledgments
We gratefully acknowledge NASA-Glenn Research Center,
Cleveland OH, for support of this work under grant no. NAG3-
2617.
Tennessee Technological University assisted in meeting the publication
costs of this article.
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